Method of synthesizing molecular sieves

ABSTRACT

The invention is directed to a method of synthesizing a molecular sieve. In particular, the invention is directed to a method for synthesizing a molecular sieve, especially a silicoaluminophosphate molecular sieve, in the presence of a templating agent and a polymeric base. The invention is also directed to formulating the molecular sieve into a catalyst useful in a process for producing olefin(s), preferably ethylene and/or propylene, from a feedstock, preferably an oxygenate containing feedstock.

RELATED APPLICATION DATA

[0001] None

FIELD OF THE INVENTION

[0002] The present invention relates to a method of synthesizing amolecular sieve. In particular, the invention is directed to a methodfor synthesizing a molecular sieve, especially a silicoaluminophosphatemolecular sieve, and to its formulation into a catalyst compositionuseful in a process for producing olefin(s), preferably ethylene and/orpropylene, from a feedstock, preferably an oxygenate containingfeedstock.

BACKGROUND OF THE INVENTION

[0003] Olefins are traditionally produced from petroleum feedstock bycatalytic or steam cracking processes. These cracking processes,especially steam cracking, produce light olefin(s) such as ethyleneand/or propylene from a variety of hydrocarbon feedstock. Ethylene andpropylene are important commodity petrochemicals useful in a variety ofprocesses for making plastics and other chemical compounds. Ethylene isused to make various polyethylene plastics, and in making otherchemicals such as vinyl chloride, ethylene oxide, ethylbenzene andalcohol. Propylene is used to make various polypropylene plastics, andin making other chemicals such as acrylonitrile and propylene oxide.

[0004] The petrochemical industry has known for some time thatoxygenates, especially alcohols, are convertible into light olefin(s).There are numerous technologies available for producing oxygenatesincluding fermentation or reaction of synthesis gas derived from naturalgas, petroleum liquids, carbonaceous materials including coal, recycledplastics, municipal waste or any other organic material. Generally, theproduction of synthesis gas involves a combustion reaction of naturalgas, mostly methane, and an oxygen source into hydrogen, carbon monoxideand/or carbon dioxide. Syngas production processes are well known, andinclude conventional steam reforming, autothermal reforming, or acombination thereof.

[0005] Methanol, the preferred alcohol for light olefin production, istypically synthesized from the catalytic reaction of hydrogen, carbonmonoxide and/or carbon dioxide in a methanol reactor in the presence ofa heterogeneous catalyst. For example, in one synthesis process methanolis produced using a copper/zinc oxide catalyst in a water-cooled tubularmethanol reactor. The preferred methanol conversion process is generallyreferred to as a methanol-to-olefin(s) process, where methanol isconverted to primarily ethylene and/or propylene in the presence of amolecular sieve.

[0006] Molecular sieves are porous solids having pores of differentsizes such as zeolites or zeolite-type molecular sieves, carbons andoxides. There are amorphous and crystalline molecular sieves. Molecularsieves include natural, mineral molecular sieves, or chemically formed,synthetic molecular sieves that are typically crystalline materialscontaining silica, and optionally alumina. The most commercially usefulmolecular sieves for the petroleum and petrochemical industries areknown as zeolites. A zeolite is an aluminosilicate having an openframework structure that usually carries negative charges. This negativecharge within portions of the framework is a result of an Al³⁺ replacinga Si⁴⁺. Cations counter-balance these negative charges preserving theelectroneutrality of the framework, and these cations are exchangeablewith other cations and/or protons. Synthetic molecular sieves,particularly zeolites, are typically synthesized by mixing sources ofalumina and silica in a strongly basic aqueous media, often in thepresence of a structure directing agent or templating agent. Thestructure of the molecular sieve formed is determined in part bysolubility of the various sources, silica-to-alumina ratio, nature ofthe cation, synthesis temperature, order of addition, type of templatingagent, and the like.

[0007] A zeolite is typically formed from comer sharing the oxygen atomsof [SiO₄] and [AlO₄] tetrahedra or octahedra. Zeolites in general have aone-, two- or three-dimensional crystalline pore structure havinguniformly sized pores of molecular dimensions that selectively adsorbmolecules that can enter the pores, and exclude those molecules that aretoo large. The pore size, pore shape, interstitial spacing or channels,composition, crystal morphology and structure are a few characteristicsof molecular sieves that determine their use in various hydrocarbonadsorption and conversion processes.

[0008] There are many different types of zeolites well known to converta feedstock, especially oxygenate containing feedstock, into one or moreolefin(s). For example, U.S. Pat. No. 5,367,100 describes the use of awell known zeolite, ZSM-5, to convert methanol into olefin(s); U.S. Pat.No. 4,062,905 discusses the conversion of methanol and other oxygenatesto ethylene and propylene using crystalline aluminosilicate zeolites,for example Zeolite T, ZK5, erionite and chabazite; and U.S. Pat. No.4,079,095 describes the use of ZSM-34 to convert methanol to hydrocarbonproducts such as ethylene and propylene.

[0009] Crystalline aluminophosphates, ALPO₄, formed from corner sharing[AlO₂] and [PO₂] tetrahedra linked by shared oxygen atoms are describedin U.S. Pat. No. 4,310,440 to produce light olefin(s) from an alcohol.Metal containing aluminophosphate molecular sieves, MeAPO's and ElAPO's,have been also described to convert alcohols into olefin(s). MeAPO'shave a [MeO₂], [AlO₂] and [PO₂] tetrahedra microporous structure, whereMe is a metal source having one or more of the divalent elements Co, Fe,Mg, Mn and Zn, and trivalent Fe from the Periodic Table of Elements.ElAPO's have an [ElO₂], [AlO₂] and [PO₂] tetrahedra microporousstructure, where El is a metal source having one or more of the elementsAs, B, Be, Ga, Ge, Li, Ti and Zr. MeAPO's and ElAPO's are typicallysynthesized by the hydrothermal crystallization of a reaction mixture ofa metal source, an aluminum source, a phosphorous source and atemplating agent. The preparation of MeAPO's and ElAPO's are found inU.S. Pat. Nos. 4,310,440, 4,500,651, 4,554,143, 4,567,029, 4,752,651,4,853,197, 4,873,390 and 5,191,141.

[0010] One of the most useful molecular sieves for converting methanolto olefin(s) are those ELAPO's or MeAPO's where the metal source issilicon, often a fumed, colloidal or precipitated silica. Thesemolecular sieves are known as silicoaluminophosphate molecular sieves.Silicoaluminophosphate (SAPO) molecular sieves contain athree-dimensional microporous crystalline framework structure of [SiO₂],[AlO₂] and [PO₂] comer sharing tetrahedral units. SAPO synthesis isdescribed in U.S. Pat. No. 4,440,871, which is herein fully incorporatedby reference. SAPO is generally synthesized by the hydrothermalcrystallization of a reaction mixture of silicon-, aluminum- andphosphorus-sources and at least one templating agent. Synthesis of aSAPO molecular sieve, its formulation into a SAPO catalyst, and its usein converting a hydrocarbon feedstock into olefin(s), particularly wherethe feedstock is methanol, is shown in U.S. Pat. Nos. 4,499,327,4,677,242, 4,677,243, 4,873,390, 5,095,163, 5,714,662 and 6,166,282, allof which are herein fully incorporated by reference.

[0011] Templating agents are used in the synthesis of molecular sieves,particularly SAPO molecular sieves, as a crystal structure-directingagent or affecting agent. Furthermore, templating agents are typicallynitrogen containing organic bases such as quaternary ammonium salts orhydroxides. Typically, because templating agents are also used tocontrol the pH during the synthesis of molecular sieves, the quaternaryammonium hydroxide is often used instead of the less expensivequaternary ammonium salt. Additionally, the quantity of the templatingagent used is often dictated by the pH of the reaction mixture in whichthe molecular sieve forms. Templating agents are typically used inexcess, relative to its incorporation in the crystalline molecular sieveproduct, in order to control the pH and/or alkaline content in thesynthesis of molecular sieves, for example as described in U.S. Pat. No.4,440,871.

[0012] The templating agent is oftentimes the most costly ingredientused in synthesizing molecular sieves. Using a second, less expensivebase as a pH controller, in addition to a templating agent, in principleleads to a reduction in the cost of synthesizing a particular molecularsieve, provided that the pH controller does not interfere with thesynthesis of the desired molecular sieve. As described in U.S. Pat. No.4,440,871 in a SAPO molecular sieve synthesis, using an inorganic baseto reduce the amount of organic templating agent, often results in theformation of undesirable dense phase products. Some organic bases, forinstance, dipropylamine, have been combined with a templating agent,tetraethylammonium hydroxide, for the synthesis of a SAPO molecularsieve. Monomeric organic bases such as dipropylamine are volatile andraise various environmental and safety concerns. Additionally, higherpressure equipment is needed for the hydrothermal synthesis of molecularsieves using volatile monomeric organic bases.

[0013] Therefore, it would be desirable to have an improved method forreducing the amount of templating agent utilized in synthesizing amolecular sieve.

SUMMARY OF THE INVENTION

[0014] This invention provides a method of synthesizing a molecularsieve, to its formulation into a molecular sieve catalyst composition,and to it use in a process, preferably a conversion process, for makingone or more olefin(s), particularly light olefin(s).

[0015] In one embodiment the invention is directed to a method forsynthesizing a molecular sieve utilizing a templating agent, preferablyan organic templating agent, and a polymeric base. In preferredembodiments, the polymeric base is a polymeric base, or a soluble and/ornon-volatile polymeric base or a non-ionic polymeric base, or acombination thereof, and most preferably the polymeric base is apolymeric imine, preferably a polyethylene imine or polyethylenimine.

[0016] In another embodiment the invention relates to a method forsynthesizing a molecular sieve, the method comprising the steps of: (a)forming a reaction mixture of at least one templating agent and at leastone of the group consisting of a silicon source, a phosphorous sourceand an aluminum source; (b) introducing to the reaction mixture anon-ionic polymeric base or a soluble polymeric base; and (c) removingthe molecular sieve from the reaction mixture. In one preferredembodiment, the polymeric base is non-volatile and/or has a pH of fromabout 8 to about 14 in an aqueous solution, and/or has an averagemolecular weight M_(W) greater than 500. In another preferred embodimentof this embodiment, the polymeric base is a polymeric imine.

[0017] In the most preferred embodiment the invention relates to amethod of synthesizing a molecular sieve, the method comprising thesteps of: (a) combining a silicon source, an aluminum source, and/or aphosphorous source; (b) introducing an organic templating agent; (c)introducing a polymeric base; and (d) removing the molecular sieve. In apreferred embodiment, the mole ratio of the organic templating agent tothe monomeric unit of the polymeric base is from about 0.01 to 1,preferably from 0.1 to 0.75, and more preferably 0.25 to 0.5.

[0018] In another embodiment of the invention the molecular sievedescribed above is formulated into a molecular sieve catalystcomposition. In this embodiment, the molecular sieve removed from step(c) above and step (d) immediately above is combined with a matrixmaterial and optionally a binder to form the molecular sieve catalystcomposition of the invention.

[0019] In yet another embodiment, the invention is directed to a processfor producing olefin(s) in the presence of any of the above molecularsieves and catalyst compositions thereof. In particular, the processinvolves producing olefin(s) in a process for converting a feedstock,preferably a feedstock containing an oxygenate, more preferably afeedstock containing an alcohol, and most preferably a feedstockcontaining methanol.

DETAILED DESCRIPTION OF THE INVENTION

[0020] Introduction

[0021] The invention is directed toward a method for synthesizing amolecular sieve using a templating agent and a polymeric base. It hasbeen found that a polymeric base is useful in combination with adecreased amount of templating agent to produce a given molecular sieve.Also, it has been found that the use of a salt as a templating agent,such as a quaternary ammonium salt, rather than the more expensivequaternary ammonium hydroxide, is useful in combination with a polymericbase to synthesize a molecular sieve. Without being bound to anyparticular theory, it is believed that the soluble or neutral polymericbase, especially a polymeric imine, more specifically apolyethylenimine, is useful to control pH, and therefore, less amount ofa basic organic templating agent, or even a non-basic organic templatingagent can be used to synthesize a particular molecular sieve.

[0022] Molecular Sieves and Catalysts Thereof

[0023] Molecular sieves have various chemical and physical, framework,characteristics. Molecular sieves have been well classified by theStructure Commission of the International Zeolite Association accordingto the rules of the IUPAC Commission on Zeolite Nomenclature. Aframework-type describes the connectivity, topology, of thetetrahedrally coordinated atoms constituting the framework, and makingan abstraction of the specific properties for those materials.Framework-type zeolite and zeolite-type molecular sieves for which astructure has been established, are assigned a three letter code and aredescribed in the Atlas of Zeolite Framework Types, 5th edition,Elsevier, London, England (2001), which is herein fully incorporated byreference.

[0024] Non-limiting examples of these molecular sieves are the smallpore molecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA,CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO,ROG, THO, and substituted forms thereof, the medium pore molecularsieves, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, andsubstituted forms thereof; and the large pore molecular sieves, EMT,FAU, and substituted forms thereof. Other molecular sieves include ANA,BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW and SOD. Non-limitingexamples of the preferred molecular sieves, particularly for convertingan oxygenate containing feedstock into olefin(s), include AEL, AFY, BEA,CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON.In one preferred embodiment, the molecular sieve of the invention has anAEI topology or a CHA topology, or a combination thereof, mostpreferably a CHA topology.

[0025] Molecular sieve materials all have 3-dimensional, four-connectedframework structure of corner-sharing TO₄ tetrahedra, where T is anytetrahedrally coordinated cation. These molecular sieves are typicallydescribed in terms of the size of the ring that defines a pore, wherethe size is based on the number of T atoms in the ring. Otherframework-type characteristics include the arrangement of rings thatform a cage, and when present, the dimension of channels, and the spacesbetween the cages. See van Bekkum, et al., Introduction to ZeoliteScience and Practice, Second Completely Revised and Expanded Edition,Volume 137, pages 1-67, Elsevier Science, B. V., Amsterdam, Netherlands(2001).

[0026] The small, medium and large pore molecular sieves have from a4-ring to a 12-ring or greater framework-type. In a preferredembodiment, the zeolitic molecular sieves have 8-, 10- or 12-ringstructures or larger and an average pore size in the range of from about3 Å to 15 Å. In the most preferred embodiment, the molecular sieves ofthe invention, preferably silicoaluminophosphate molecular sieves have8-rings and an average pore size less than about 5 Å, preferably in therange of from 3 Å to about 5 Å, more preferably from 3 Å to about 4.5 Å,and most preferably from 3.5 Å to about 4.2 Å.

[0027] Molecular sieves, particularly zeolitic and zeolitic-typemolecular sieves, preferably have a molecular framework of one,preferably two or more corner-sharing [TO₄] tetrahedral units, morepreferably, two or more [SiO₄], [AlO₄] and/or [PO₄] tetrahedral units,and most preferably [SiO₄], [AlO₄] and [PO₄] tetrahedral units. Thesesilicon, aluminum, and phosphorous based molecular sieves and metalcontaining silicon, aluminum and phosphorous based molecular sieves havebeen described in detail in numerous publications including for example,U.S. Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat.No. 4,440,871 (SAPO), European Patent Application EP-A-0 159 624 (ELAPSOwhere El is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S.Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217,4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO,EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg,Mn, Ti or Zn), U.S. Pat. No. 4,310,440 (AlPO₄), EP-A-0 158 350(SENAPSO), U.S. Pat. No. 4,973,460 (LiAPSO), U.S. Pat. No. 4,789,535(LiAPO), U.S. Pat. No. 4,992,250 (GeAPSO), U.S. Pat. No. 4,888,167(GeAPO), U.S. Pat. No. 5,057,295 (BAPSO), U.S. Pat. No. 4,738,837(CrAPSO), U.S. Pat. Nos. 4,759,919, and 4,851,106 (CrAPO), U.S. Pat.Nos. 4,758,419, 4,882,038, 5,434,326 and 5,478,787 (MgAPSO), U.S. Pat.No. 4,554,143 (FeAPO), U.S. Pat. No. 4,894,213 (AsAPSO), U.S. Pat. No.4,913,888 (AsAPO), U.S. Pat. Nos. 4,686,092, 4,846,956 and 4,793,833(MnAPSO), U.S. Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No.4,737,353 (BeAPSO), U.S. Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos.4,801,309, 4,684,617 and 4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651,4,551,236 and 4,605,492 (TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970(CoAPSO), U.S. Pat. No. 4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, whereQ is framework oxide unit [QO₂]), as well as U.S. Pat. Nos. 4,567,029,4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876,4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,241,093, 5,493,066 and5,675,050, all of which are herein fully incorporated by reference.

[0028] Other molecular sieves include those described in EP-0 888 187 B1(microporous crystalline metallophosphates, SAPO₄ (UIO-6)), U.S. Pat.No. 6,004,898 (molecular sieve and an alkaline earth metal), U.S. patentapplication Ser. No. 09/511,943 filed Feb. 24, 2000 (integratedhydrocarbon co-catalyst), PCT WO 01/64340 published Sep. 7, 2001(thoriumcontaining molecular sieve), and R. Szostak, Handbook of MolecularSieves, Van Nostrand Reinhold, New York, N.Y. (1992), which are allherein fully incorporated by reference.

[0029] The more preferred silicon, aluminum and/or phosphorouscontaining molecular sieves, and aluminum, phosphorous, and optionallysilicon, containing molecular sieves include aluminophosphate (ALPO)molecular sieves and silicoaluminophosphate (SAPO) molecular sieves andsubstituted, preferably metal substituted, ALPO and SAPO molecularsieves. The most preferred molecular sieves are SAPO molecular sieves,and metal substituted SAPO molecular sieves. In an embodiment, the metalis an alkali metal of Group IA of the Periodic Table of Elements, analkaline earth metal of Group IIA of the Periodic Table of Elements, arare earth metal of Group IIIB, including the Lanthanides: lanthanum,cerium, praseodymium, neodymium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;and scandium or yttrium of the Periodic Table of Elements, a transitionmetal of Groups IVB, VB, VIB, VIIB, VIIIB, and IB of the Periodic Tableof Elements, or mixtures of any of these metal species. In one preferredembodiment, the metal is selected from the group consisting of Co, Cr,Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr, and mixtures thereof. Inanother preferred embodiment, these metal atoms discussed above areinserted into the framework of a molecular sieve through a tetrahedralunit, such as [MeO₂], and carry a net charge depending on the valencestate of the metal substituent. For example, in one embodiment, when themetal substituent has a valence state of +2, +3, +4, +5, or +6, the netcharge of the tetrahedral unit is between −2 and +2.

[0030] In one embodiment, the molecular sieve, as described in many ofthe U.S. Patents mentioned above, is represented by the empiricalformula, on an anhydrous basis:

mR:(M_(x)Al_(y)P_(z))O₂

[0031] wherein R represents at least one templating agent, preferably anorganic templating agent; m is the number of moles of R per mole of(M_(x)Al_(y)P_(z))O₂ and m has a value from 0 to 1, preferably 0 to 0.5,and most preferably from 0 to 0.3; x, y, and z represent the molefraction of Al, P and M as tetrahedral oxides, where M is a metalselected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIBand Lanthanide's of the Periodic Table of Elements, preferably M isselected from one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg,Mn, Ni, Sn, Ti, Zn and Zr. In an embodiment, m is greater than or equalto 0.2, and x, y and z are greater than or equal to 0.01.

[0032] In another embodiment, m is greater than 0.1 to about 1, x isgreater than 0 to about 0.25, y is in the range of from 0.4 to 0.5, andz is in the range of from 0.25 to 0.5, more preferably m is from 0.15 to0.7, x is from 0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to0.5.

[0033] Non-limiting examples of SAPO and ALPO molecular sieves of theinvention include one or a combination of SAPO-5, SAPO-8, SAPO-11,SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36,SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Pat. No. 6,162,415),SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36,ALPO-37, ALPO-46, and metal containing molecular sieves thereof. Themore preferred zeolite-type molecular sieves include one or acombination of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 andALPO-34, even more preferably one or a combination of SAPO-18, SAPO-34,ALPO-34 and ALPO-18, and metal containing molecular sieves thereof, andmost preferably one or a combination of SAPO-34 and ALPO-18, and metalcontaining molecular sieves thereof.

[0034] In an embodiment, the molecular sieve is an intergrowth materialhaving two or more distinct phases of crystalline structures within onemolecular sieve composition. In particular, intergrowth molecular sievesare described in the U.S. patent application Ser. No. 09/924,016 filedAug. 7, 2001 and PCT WO 98/15496 published Apr. 16, 1998, both of whichare herein fully incorporated by reference. In another embodiment, themolecular sieve comprises at least one intergrown phase of AEI and CHAframework-types. For example, SAPO-18, ALPO-18 and RUW-18 have an AEIframework-type, and SAPO-34 has a CHA framework-type.

[0035] Molecular Sieve Synthesis

[0036] The synthesis of molecular sieves is described in many of thereferences discussed above. Generally, molecular sieves are synthesizedby the hydrothermal crystallization of one or more of a source ofaluminum, a source of phosphorous, a source of silicon, a templatingagent, and a metal containing compound. Typically, a combination ofsources of silicon, aluminum and phosphorous, optionally with one ormore templating agents and/or one or more metal containing compounds areplaced in a sealed pressure vessel, optionally lined with an inertplastic such as polytetrafluoroethylene, and heated, under acrystallization pressure and temperature, until a crystalline materialis formed, and then recovered by filtration, centrifugation and/ordecanting.

[0037] In a preferred embodiment the molecular sieves are synthesized byforming a reaction product of a source of silicon, a source of aluminum,a source of phosphorous, an organic templating agent, preferably anitrogen containing organic templating agent, and one or more polymericbases. This particularly preferred embodiment results in the synthesisof a silicoaluminophosphate crystalline material that is then isolatedby filtration, centrifugation and/or decanting.

[0038] Non-limiting examples of silicon sources include a silicates,fumed silica, for example, Aerosil-200 available from Degussa Inc., NewYork, N.Y., and CAB-O-SIL M-5, silicon compounds such as tetraalkylorthosilicates, for example, tetramethyl orthosilicate (TMOS) andtetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensionsthereof, for example Ludox-HS-40 sol available from E. I. du Pont deNemours, Wilmington, Del., silicic acid, alkali-metal silicate, or anycombination thereof. The preferred source of silicon is a silica sol.

[0039] Non-limiting examples of aluminum sources includealuminum-containing compositions such as aluminum alkoxides, for examplealuminum isopropoxide, aluminum phosphate, aluminum hydroxide, sodiumaluminate, pseudo-boehmite, gibbsite and aluminum trichloride, or anycombinations thereof. A preferred source of aluminum is pseudo-boehmite,particularly when producing a silicoaluminophosphate molecular sieve.

[0040] Non-limiting examples of phosphorous sources, which may alsoinclude aluminum-containing phosphorous compositions, includephosphorous-containing, inorganic or organic, compositions such asphosphoric acid, organic phosphates such as triethyl phosphate, andcrystalline or amorphous aluminophosphates such as ALPO₄, phosphoroussalts, or combinations thereof. The preferred source of phosphorous isphosphoric acid, particularly when producing a silicoaluminophosphate.

[0041] Templating agents are generally compounds that contain elementsof Group VA of the Periodic Table of Elements, particularly nitrogen,phosphorus, arsenic and antimony, more preferably nitrogen orphosphorous, and most preferably nitrogen. Typical templating agents ofGroup VA of the Periodic Table of elements also contain at least onealkyl or aryl group, preferably an alkyl or aryl group having from 1 to10 carbon atoms, and more preferably from 1 to 8 carbon atoms. Thepreferred templating agents are nitrogen-containing compounds such asamines and quaternary ammonium compounds.

[0042] The quaternary ammonium compounds, in one embodiment, arerepresented by the general formula R₄N⁺, where each R is hydrogen or ahydrocarbyl or substituted hydrocarbyl group, preferably an alkyl groupor an aryl group having from 1 to 10 carbon atoms. In one embodiment,the templating agents include a combination of one or more quaternaryammonium compound(s) and one or more of a mono-, di- or tri-amine.

[0043] Non-limiting examples of templating agents include tetraalkylammonium compounds including salts thereof such as tetramethyl ammoniumcompounds including salts thereof, tetraethyl ammonium compoundsincluding salts thereof, tetrapropyl ammonium including salts thereof,and tetrabutylammonium including salts thereof, cyclohexylamine,morpholine, di-n-propylamine (DPA), tripropylamine, triethylamine (TEA),triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine,N,N-dimethylbenzylamine, N,N-diethylethanolamine, dicyclohexylamine,N,N-dimethylethanolamine, choline, N,N′-dimethylpiperazine,1,4-diazabicyclo(2,2,2)octane, N′,N′,N,N-tetramethyl(1,6)hexanediamine,N-methyldiethanolamine, N-methyl-ethanolamine, N-methyl piperidine,3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methyl-pyridine, quinuclidine, N,N′-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine, di-n-pentylamine,isopropylamine, t-butylamine, ethylenediamine, pyrrolidine, and2-imidazolidone.

[0044] The preferred templating agent or template is atetraethylammonium compound, such as tetraethyl ammonium hydroxide(TEAOH), tetraethyl ammonium phosphate, tetraethyl ammonium fluoride,tetraethyl ammonium bromide, tetraethyl ammonium chloride and tetraethylammonium acetate. The most preferred templating agent is tetraethylammonium hydroxide and salts thereof, particularly when producing asilicoaluminophosphate molecular sieve. In one embodiment, a combinationof two or more of any of the above templating agents is used incombination with one or more of a silicon-, aluminum-, andphosphorous-source, and a polymeric base.

[0045] Polymeric bases, especially polymeric bases that are soluble ornon-ionic, useful in the invention, are those having a pH sufficient tocontrol the pH desired for synthesizing a given molecular sieve,especially a SAPO molecular sieve. In a preferred embodiment, thepolymeric base is soluble or the polymeric base is non-ionic, preferablythe polymeric base is a non-ionic and soluble polymeric base, and mostpreferably the polymeric base is a polymeric imine. In one embodiment,the polymeric base of the invention has a pH in an aqueous solution,preferably water, from greater than 7 to about 14, more preferably fromabout 8 to about 14, most preferably from about 9 to 14.

[0046] In another embodiment, the non-volatile polymeric base isrepresented by the formula: (R—NH)_(x), where (R—NH) is a polymeric ormonomeric unit where R contains from 1 to 20 carbon atoms, preferablyfrom 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, andmost preferably from 1 to 4 carbon atoms; x is an integer from 1 to500,000. In one embodiment, R is a linear, branched, or cyclic polymer,monomeric, chain, preferably a linear polymer chain having from 1 to 20carbon atoms.

[0047] In another embodiment, the polymeric base is a water misciblepolymeric base, preferably in an aqueous solution. In yet anotherembodiment, the polymeric base is a polyethylenimine that is representedby the following general formula:

(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n)),

[0048] wherein m is from 10 to 20,000, and n is from 0 to 2,000,preferably from 1 to 2000.

[0049] In another embodiment, the polymeric base of the invention has aaverage molecular weight from about 500 to about 1,000,000, preferablyfrom about 2,000 to about 800,000, more preferably from about 10,000 toabout 750,000, and most preferably from about 50,000 to about 750,000.

[0050] In another embodiment, the mole ratio of the monomeric unit ofthe polymeric base of the invention, containing one basic group, to thetemplating agent(s) is less than 20, preferably less than 12, morepreferably less than 10, even more preferably less than 8, still evenmore preferably less than 5, and most preferably less than 4.

[0051] Non-limiting examples of polymer bases include: epichlorohydrinmodified polyethylenimine, ethoxylated polyethylenimine,polypropylenimine diamine dendrimers (DAB-Am-n), poly(allylamine)[CH₂CH(CH₂NH₂)]_(n), poly(1,2-dihydro-2,2,4-trimethylquinoline), andpoly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).

[0052] In another embodiment the invention is directed to a method forsynthesizing a molecular sieve utilizing a templating agent, preferablyan organic templating agent such as an organic amine, an ammonium saltand/or an ammonium hydroxide, in combination with a polymeric base suchas polyethylenimine.

[0053] In a typical synthesis of the molecular sieve, the phosphorous-,aluminum-, and/or silicon-containing components are mixed, preferablywhile stirring and/or agitation and/or seeding with a crystallinematerial, optionally with an alkali metal, in a solvent such as water,and one or more templating agents and a polymeric base, to form asynthesis mixture that is then heated under crystallization conditionsof pressure and temperature as described in U.S. Pat. Nos. 4,440,871,4,861,743, 5,096,684, and 5,126,308, which are all herein fullyincorporated by reference. The polymeric base is combined with the atleast one templating agent, and one or more of the aluminum source,phosphorous source, and silicon source, in any order, for example,simultaneously with one or more of the sources, premixed with one ormore of the sources and/or templating agent, after combining the sourcesand the templating agent, and the like.

[0054] Generally, the synthesis mixture described above is sealed in avessel and heated, preferably under autogenous pressure, to atemperature in the range of from about 80° C. to about 250° C.,preferably from about 100° C. to about 250° C., more preferably fromabout 125° C. to about 225° C., even more preferably from about 150° C.to about 180° C. In another embodiment, the hydrothermal crystallizationtemperature is less than 225° C., preferably less than 200° C. to about80° C., and more preferably less than 195° C. to about 100° C.

[0055] In yet another embodiment, the crystallization temperature isincreased gradually or stepwise during synthesis, preferably thecrystallization temperature is maintained constant, for a period of timeeffective to form a crystalline product. The time required to form thecrystalline product is typically from immediately up to several weeks,the duration of which is usually dependent on the temperature; thehigher the temperature the shorter the duration. In one embodiment, thecrystalline product is formed under heating from about 30 minutes toaround 2 weeks, preferably from about 45 minutes to about 240 hours, andmore preferably from about 1 hour to about 120 hours.

[0056] In one embodiment, the synthesis of a molecular sieve is aided byseeds from another or the same framework type molecular sieve.

[0057] The hydrothermal crystallization is carried out with or withoutagitation or stirring, for example stirring or tumbling. The stirring oragitation during the crystallization period may be continuous orintermittent, preferably continuous agitation. Typically, thecrystalline molecular sieve product is formed, usually in a slurrystate, and is recovered by any standard technique well known in the art,for example centrifugation or filtration. The isolated or separatedcrystalline product, in an embodiment, is washed, typically, using aliquid such as water, from one to many times. The washed crystallineproduct is then optionally dried, preferably in air.

[0058] One method for crystallization involves subjecting an aqueousreaction mixture containing an excess amount of a templating agent andpolymeric base, subjecting the mixture to crystallization underhydrothermal conditions, establishing an equilibrium between molecularsieve formation and dissolution, and then, removing some of the excesstemplating agent and/or organic base to inhibit dissolution of themolecular sieve. See for example U.S. Pat. No. 5,296,208, which isherein fully incorporated by reference.

[0059] Another method of crystallization is directed to not stirring areaction mixture, for example a reaction mixture containing at aminimum, a silicon-, an aluminum-, and/or a phosphorous-composition,with a templating agent and a polymeric base, for a period of timeduring crystallization. See PCT WO 01/47810 published Jul. 5, 2001,which is herein fully incorporated by reference.

[0060] Other methods for synthesizing molecular sieves or modifyingmolecular sieves are described in U.S. Pat. No. 5,879,655 (controllingthe ratio of the templating agent to phosphorous), U.S. Pat. No.6,005,155 (use of a modifier without a salt), U.S. Pat. No. 5,475,182(acid extraction), U.S. Pat. No. 5,962,762 (treatment with transitionmetal), U.S. Pat. Nos. 5,925,586 and 6,153,552 (phosphorous modified),U.S. Pat. No. 5,925,800 (monolith supported), U.S. Pat. No. 5,932,512(fluorine treated), U.S. Pat. No. 6,046,373 (electromagnetic wavetreated or modified), U.S. Pat. No. 6,051,746 (polynuclear aromaticmodifier), U.S. Pat. No. 6,225,254 (heating template), PCT WO 01/36329published May 25, 2001 (surfactant synthesis), PCT WO 01/25151 publishedApr. 12, 2001 (staged acid addition), PCT WO 01/60746 published Aug. 23,2001 (silicon oil), U.S. patent application Ser. No. 09/929,949 filedAug. 15, 2001 (cooling molecular sieve), U.S. patent application Ser.No. 09/615,526 filed Jul. 13, 2000 (metal impregnation includingcopper), U.S. patent application Ser. No. 09/672,469 filed Sep. 28, 2000(conductive microfilter), and U.S. patent application Ser. No.09/754,812 filed Jan. 4, 2001 (freeze drying the molecular sieve), whichare all herein fully incorporated by reference.

[0061] In one preferred embodiment, when a templating agent is used inthe synthesis of a molecular sieve, it is preferred that the templatingagent is substantially, preferably completely, removed aftercrystallization by numerous well known techniques, for example, heattreatments such as calcination. Calcination involves contacting themolecular sieve containing the templating agent with a gas, preferablycontaining oxygen, at any desired concentration at an elevatedtemperature sufficient to either partially or completely decompose andoxidize the templating agent.

[0062] Molecular sieve have either a high silicon (Si) to aluminum (Al)ratio or a low silicon to aluminum ratio, however, a low Si/Al ratio ispreferred for SAPO synthesis. In one embodiment, the molecular sieve hasa Si/Al ratio less than 0.65, preferably less than 0.40, more preferablyless than 0.32, and most preferably less than 0.20. In anotherembodiment the molecular sieve has a Si/Al ratio in the range of fromabout 0.65 to about 0.10, preferably from about 0.40 to about 0.10, morepreferably from about 0.32 to about 0.10, and more preferably from about0.32 to about 0.15.

[0063] The pH of a reaction mixture containing at a minimum a silicon-,aluminum-, and/or phosphorous-composition, a templating agent, and apolymeric base should be in the range of from 2 to 10, preferably in therange of from 4 to 9, and most preferably in the range of from 5 to 8.The pH can be controlled by the addition of basic or acidic compounds asnecessary to maintain the pH during the synthesis in the preferred rangeof from 4 to 9. In another embodiment, the templating agent and/orpolymeric base is added to the reaction mixture of the silicon sourceand phosphorous source such that the pH of the reaction mixture does notexceed 10.

[0064] In one embodiment, the molecular sieves of the invention arecombined with one or more other molecular sieves. In another embodiment,the preferred silicoaluminophosphate or aluminophosphate molecularsieves, or a combination thereof, are combined with one more of thefollowing non-limiting examples of molecular sieves described in thefollowing: Beta (U.S. Pat. No. 3,308,069), ZSM-5 (U.S. Pat. Nos.3,702,886, 4,797,267 and 5,783,321), ZSM-11 (U.S. Pat. No. 3,709,979),ZSM-12 (U.S. Pat. No. 3,832,449), ZSM-12 and ZSM-38 (U.S. Pat. No.3,948,758), ZSM-22 (U.S. Pat. No. 5,336,478), ZSM-23 (U.S. Pat. No.4,076,842), ZSM-34 (U.S. Pat. No. 4,086,186), ZSM-35 (U.S. Pat. No.4,016,245, ZSM-48 (U.S. Pat. No. 4,397,827), ZSM-58 (U.S. Pat. No.4,698,217), MCM-1 (U.S. Pat. No. 4,639,358), MCM-2 (U.S. Pat. No.4,673,559), MCM-3 (U.S. Pat. No. 4,632,811), MCM-4 (U.S. Pat. No.4,664,897), MCM-5 (U.S. Pat. No. 4,639,357), MCM-9 (U.S. Pat. No.4,880,611), MCM-10 (U.S. Pat. No. 4,623,527), MCM-14 (U.S. Pat. No.4,619,818), MCM-22 (U.S. Pat. No. 4,954,325), MCM-41 (U.S. Pat. No.5,098,684), M-41S (U.S. Pat. No. 5,102,643), MCM-48 (U.S. Pat. No.5,198,203), MCM-49 (U.S. Pat. No. 5,236,575), MCM-56 (U.S. Pat. No.5,362,697), ALPO-11 (U.S. Pat. No. 4,310,440), titanium aluminosilicates(TASO), TASO-45 (EP-A-0 229,-295), boron silicates (U.S. Pat. No.4,254,297), titanium aluminophosphates (TAPO) (U.S. Pat. No. 4,500,651),mixtures of ZSM-5 and ZSM-11 (U.S. Pat. No. 4,229,424), ECR-18 (U.S.Pat. No. 5,278,345), SAPO-34 bound ALPO-5 (U.S. Pat. No. 5,972,203), PCTWO 98/57743 published Dec. 23, 1988 (molecular sieve andFischer-Tropsch), U.S. Pat. No. 6,300,535 (MFI-bound zeolites), andmesoporous molecular sieves (U.S. Pat. Nos. 6,284,696, 5,098,684,5,102,643 and 5,108,725), which are all herein fully incorporated byreference.

[0065] Method for Making Molecular Sieve Catalyst Compositions

[0066] Once the molecular sieve is synthesized, depending on therequirements of the particular conversion process, the molecular sieveis then formulated into a molecular sieve catalyst composition,particularly for commercial use. The molecular sieves synthesized aboveare made or formulated into catalysts by combining the synthesizedmolecular sieves with a binder and/or a matrix material to form amolecular sieve catalyst composition or a formulated molecular sievecatalyst composition. This formulated molecular sieve catalystcomposition is formed into useful shape and sized particles bywell-known techniques such as spray drying, pelletizing, extrusion, andthe like.

[0067] There are many different binders that are useful in forming themolecular sieve catalyst composition. Non-limiting examples of bindersthat are useful alone or in combination include various types ofhydrated alumina, silicas, and/or other inorganic oxide sol. Onepreferred alumina containing sol is aluminum chlorhydrol. The inorganicoxide sol acts like glue binding the synthesized molecular sieves andother materials such as the matrix together, particularly after thermaltreatment. Upon heating, the inorganic oxide sol, preferably having alow viscosity, is converted into an inorganic oxide matrix component.For example, an alumina sol will convert to an aluminum oxide matrixfollowing heat treatment.

[0068] Aluminum chlorhydrol, a hydroxylated aluminum based solcontaining a chloride counter ion, has the general formula ofAl_(m)O_(n)(OH)_(o)Cl_(p).x(H₂O) wherein m is 1 to 20, n is 1 to 8, o is5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binderis Al₁₃O₄(OH)₂₄Cl₇.12(H₂O) as is described in G. M. Wolterman, et al.,Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993), which is hereinincorporated by reference. In another embodiment, one or more bindersare combined with one or more other non-limiting examples of aluminamaterials such as aluminum oxyhydroxide, γ-alumina, boehmite, diaspore,and transitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina, aluminum trihydroxide,such as gibbsite, bayerite, nordstrandite, doyelite, and mixturesthereof.

[0069] In another embodiment, the binders are alumina sols,predominantly comprising aluminum oxide, optionally including somesilicon. In yet another embodiment, the binders are peptized aluminamade by treating alumina hydrates such as pseudobohemite, with an acid,preferably an acid that does not contain a halogen, to prepare sols oraluminum ion solutions. Non-limiting examples of commercially availablecolloidal alumina sols include Nalco 8676 available from Nalco ChemicalCo., Naperville, Ill., and Nyacol available from The PQ Corporation,Valley Forge, Pa.

[0070] The molecular sieve synthesized above, in a preferred embodiment,is combined with one or more matrix material(s). Matrix materials aretypically effective in reducing overall catalyst cost, act as thermalsinks assisting in shielding heat from the catalyst composition forexample during regeneration, densifying the catalyst composition,increasing catalyst strength such as crush strength and attritionresistance, and to control the rate of conversion in a particularprocess.

[0071] Non-limiting examples of matrix materials include one or more of:rare earth metals, metal oxides including titania, zirconia, magnesia,thoria, beryllia, quartz, silica or sols, and mixtures thereof, forexample silica-magnesia, silica-zirconia, silica-titania, silica-aluminaand silica-alumina-thoria. In an embodiment, matrix materials arenatural clays such as those from the families of montmorillonite andkaolin. These natural clays include sabbentonites and those kaolinsknown as, for example, Dixie, McNamee, Georgia and Florida clays.Non-limiting examples of other matrix materials include: haloysite,kaolinite, dickite, nacrite, or anauxite. In one embodiment, the matrixmaterial, preferably any of the clays, are subjected to well knownmodification processes such as calcination and/or acid treatment and/orchemical treatment.

[0072] In one preferred embodiment, the matrix material is a clay or aclay-type composition, preferably the clay or clay-type compositionhaving a low iron or titania content, and most preferably the matrixmaterial is kaolin. Kaolin has been found to form a pumpable, high solidcontent slurry, it has a low fresh surface area, and it packs togethereasily due to its platelet structure. A preferred average particle sizeof the matrix material, most preferably kaolin, is from about 0.1 μm toabout 0.6 μm with a D90 particle size distribution of less than about 1μm.

[0073] In one embodiment, the binder, the molecular sieve and the matrixmaterial are combined in the presence of a liquid to form a molecularsieve catalyst composition, where the amount of binder is from about 2%by weight to about 30% by weight, preferably from about 5% by weight toabout 20% by weight, and more preferably from about 7% by weight toabout 15% by weight, based on the total weight of the binder, themolecular sieve and matrix material, excluding the liquid (aftercalcination).

[0074] In another embodiment, the weight ratio of the binder to thematrix material used in the formation of the molecular sieve catalystcomposition is from 0:1 to 1:15, preferably 1:15 to 1:5, more preferably1:10 to 1:4, and most preferably 1:6 to 1:5. It has been found that ahigher sieve content, lower matrix content, increases the molecularsieve catalyst composition performance, however, lower sieve content,higher matrix material, improves the attrition resistance of thecomposition.

[0075] Upon combining the molecular sieve and the matrix material,optionally with a binder, in a liquid to form a slurry, mixing,preferably rigorous mixing is needed to produce a substantiallyhomogeneous mixture containing the molecular sieve. Non-limitingexamples of suitable liquids include one or a combination of water,alcohol, ketones, aldehydes, and/or esters. The most preferred liquid iswater. In one embodiment, the slurry is colloid-milled for a period oftime sufficient to produce the desired slurry texture, sub-particlesize, and/or sub-particle size distribution.

[0076] The molecular sieve and matrix material, and the optional binder,are in the same or different liquid, and are combined in any order,together, simultaneously, sequentially, or a combination thereof. In thepreferred embodiment, the same liquid, preferably water is used. Themolecular sieve, matrix material, and optional binder, are combined in aliquid as solids, substantially dry or in a dried form, or as slurries,together or separately. If solids are added together as dry orsubstantially dried solids, it is preferable to add a limited and/orcontrolled amount of liquid.

[0077] In one embodiment, the slurry of the molecular sieve, binder andmatrix materials is mixed or milled to achieve a sufficiently uniformslurry of sub-particles of the molecular sieve catalyst composition thatis then fed to a forming unit that produces the molecular sieve catalystcomposition. In a preferred embodiment, the forming unit is spray dryer.Typically, the forming unit is maintained at a temperature sufficient toremove most of the liquid from the slurry, and from the resultingmolecular sieve catalyst composition. The resulting catalyst compositionwhen formed in this way takes the form of microspheres.

[0078] When a spray drier is used as the forming unit, typically, theslurry of the molecular sieve and matrix material, and optionally abinder, is co-fed to the spray drying volume with a drying gas with anaverage inlet temperature ranging from 200° C. to 550° C., and acombined outlet temperature ranging from 100° C. to about 225° C. In anembodiment, the average diameter of the spray dried formed catalystcomposition is from about 40 μm to about 300 μm, preferably from about50 μm to about 250 μm, more preferably from about 50 μm to about 200 μm,and most preferably from about 65 μm to about 90 μm.

[0079] During spray drying, the slurry is passed through a nozzledistributing the slurry into small droplets, resembling an aerosol sprayinto a drying chamber. Atomization is achieved by forcing the slurrythrough a single nozzle or multiple nozzles with a pressure drop in therange of from 100 psia to 1000 psia (690 kPaa to 6895 kPaa). In anotherembodiment, the slurry is co-fed through a single nozzle or multiplenozzles along with an atomization fluid such as air, steam, flue gas, orany other suitable gas.

[0080] In yet another embodiment, the slurry described above is directedto the perimeter of a spinning wheel that distributes the slurry intosmall droplets, the size of which is controlled by many factorsincluding slurry viscosity, surface tension, flow rate, pressure, andtemperature of the slurry, the shape and dimension of the nozzle(s), orthe spinning rate of the wheel. These droplets are then dried in aco-current or counter-current flow of air passing through a spray drierto form a substantially dried or dried molecular sieve catalystcomposition, more specifically a molecular sieve in powder form.

[0081] Generally, the size of the powder is controlled to some extent bythe solids content of the slurry. However, control of the size of thecatalyst composition and its spherical characteristics are controllableby varying the slurry feed properties and conditions of atomization.

[0082] Other methods for forming a molecular sieve catalyst compositionis described in U.S. patent application Ser. No. 09/617,714 filed Jul.17, 2000 (spray drying using a recycled molecular sieve catalystcomposition), which is herein incorporated by reference.

[0083] In another embodiment, the formulated molecular sieve catalystcomposition contains from about 1% to about 99%, more preferably fromabout 5% to about 90%, and most preferably from about 10% to about 80%,by weight of the molecular sieve based on the total weight of themolecular sieve catalyst composition.

[0084] In another embodiment, the weight percent of binder in or on thespray dried molecular sieve catalyst composition based on the totalweight of the binder, molecular sieve, and matrix material is from about2% by weight to about 30% by weight, preferably from about 5% by weightto about 20% by weight, and more preferably from about 7% by weight toabout 15% by weight.

[0085] Once the molecular sieve catalyst composition is formed in asubstantially dry or dried state, to further harden and/or activate theformed catalyst composition, a heat treatment such as calcination, at anelevated temperature is usually performed. A conventional calcinationenvironment is air that typically includes a small amount of watervapor. Typical calcination temperatures are in the range from about 400°C. to about 1,000° C., preferably from about 500° C. to about 800° C.,and most preferably from about 550° C. to about 700° C., preferably in acalcination environment such as air, nitrogen, helium, flue gas(combustion product lean in oxygen), or any combination thereof.

[0086] In one embodiment, calcination of the formulated molecular sievecatalyst composition is carried out in any number of well known devicesincluding rotary calciners, fluid bed calciners, batch ovens, and thelike. Calcination time is typically dependent on the degree of hardeningof the molecular sieve catalyst composition and the temperature rangesfrom about 15 minutes to about 2 hours.

[0087] In a preferred embodiment, the molecular sieve catalystcomposition is heated in nitrogen at a temperature of from about 600° C.to about 700° C. Heating is carried out for a period of time typicallyfrom 30 minutes to 15 hours, preferably from 1 hour to about 10 hours,more preferably from about 1 hour to about 5 hours, and most preferablyfrom about 2 hours to about 4 hours.

[0088] Other methods for activating a molecular sieve catalystcomposition, in particular where the molecular sieve is a reactionproduct of the combination of a silicon-, phosphorous-, andaluminum-sources, a templating agent, and a polymeric base, moreparticularly a silicoaluminophosphate catalyst composition (SAPO) aredescribed in, for example, U.S. Pat. No. 5,185,310 (heating molecularsieve of gel alumina and water to 450° C.), PCT WO 00/75072 publishedDec. 14, 2000 (heating to leave an amount of template), and U.S.application Ser. No. 09/558,774 filed Apr. 26, 2000 (rejuvenation ofmolecular sieve), which are all herein fully incorporated by reference.

[0089] Process for Using the Molecular Sieve Catalyst Compositions

[0090] The molecular sieve catalysts and compositions described aboveare useful in a variety of processes including: cracking, of for examplea naphtha feed to light olefin(s) (U.S. Pat. No. 6,300,537) or highermolecular weight (MW) hydrocarbons to lower MW hydrocarbons;hydrocracking, of for example heavy petroleum and/or cyclic feedstock;isomerization, of for example aromatics such as xylene, polymerization,of for example one or more olefin(s) to produce a polymer product;reforming; hydrogenation; dehydrogenation; dewaxing, of for examplehydrocarbons to remove straight chain paraffins; absorption, of forexample alkyl aromatic compounds for separating out isomers thereof;alkylation, of for example aromatic hydrocarbons such as benzene andalkyl benzene, optionally with propylene to produce cumeme or with longchain olefins; transalkylation, of for example a combination of aromaticand polyalkylaromatic hydrocarbons; dealkylation; hydrodecylization;disproportionation, of for example toluene to make benzene andparaxylene; oligomerization, of for example straight and branched chainolefin(s); and dehydrocyclization.

[0091] Preferred processes are conversion processes including: naphthato highly aromatic mixtures; light olefin(s) to gasoline, distillatesand lubricants; oxygenates to olefin(s); light paraffins to olefinsand/or aromatics; and unsaturated hydrocarbons (ethylene and/oracetylene) to aldehydes for conversion into alcohols, acids and esters.The most preferred process of the invention is a process directed to theconversion of a feedstock comprising one or more oxygenates to one ormore olefin(s).

[0092] The molecular sieve catalyst compositions described above areparticularly useful in conversion processes of different feedstock.Typically, the feedstock contains one or more aliphatic-containingcompounds that include alcohols, amines, carbonyl compounds for examplealdehydes, ketones and carboxylic acids, ethers, halides, mercaptans,sulfides, and the like, and mixtures thereof. The aliphatic moiety ofthe aliphatic-containing compounds typically contains from 1 to about 50carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.

[0093] Non-limiting examples of aliphatic-containing compounds include:alcohols such as methanol and ethanol, alkyl-mercaptans such as methylmercaptan and ethyl mercaptan, alkyl-sulfides such as methyl sulfide,alkyl-amines such as methyl amine, alkyl-ethers such as dimethyl ether,diethyl ether and methylethyl ether, alkyl-halides such as methylchloride and ethyl chloride, alkyl ketones such as dimethyl ketone,formaldehydes, and various acids such as acetic acid.

[0094] In a preferred embodiment of the process of the invention, thefeedstock contains one or more oxygenates, more specifically, one ormore organic compound(s) containing at least one oxygen atom. In themost preferred embodiment of the process of invention, the oxygenate inthe feedstock is one or more alcohol(s), preferably aliphatic alcohol(s)where the aliphatic moiety of the alcohol(s) has from 1 to 20 carbonatoms, preferably from 1 to 10 carbon atoms, and most preferably from 1to 4 carbon atoms. The alcohols useful as feedstock in the process ofthe invention include lower straight and branched chain aliphaticalcohols and their unsaturated counterparts.

[0095] Non-limiting examples of oxygenates include methanol, ethanol,n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethylether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethylketone, acetic acid, and mixtures thereof.

[0096] In the most preferred embodiment, the feedstock is selected fromone or more of methanol, ethanol, dimethyl ether, diethyl ether or acombination thereof, more preferably methanol and dimethyl ether, andmost preferably methanol.

[0097] The various feedstocks discussed above, particularly a feedstockcontaining an oxygenate, more particularly a feedstock containing analcohol, is converted primarily into one or more olefin(s). Theolefin(s) or olefin monomer(s) produced from the feedstock typicallyhave from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, morepreferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbonsatoms, and most preferably ethylene an/or propylene.

[0098] Non-limiting examples of olefin monomer(s) include ethylene,propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1and decene-1, preferably ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and isomers thereof. Other olefinmonomer(s) include unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins.

[0099] In the most preferred embodiment, the feedstock, preferably ofone or more oxygenates, is converted in the presence of a molecularsieve catalyst composition into olefin(s) having 2 to 6 carbons atoms,preferably 2 to 4 carbon atoms. Most preferably, the olefin(s), alone orcombination, are converted from a feedstock containing an oxygenate,preferably an alcohol, most preferably methanol, to the preferredolefin(s) ethylene and/or propylene.

[0100] The are many processes used to convert feedstock into olefin(s)including various cracking processes such as steam cracking, thermalregenerative cracking, fluidized bed cracking, fluid catalytic cracking,deep catalytic cracking, and visbreaking.

[0101] The most preferred process is generally referred to asgas-to-olefins (GTO) or alternatively, methanol-to-olefins (MTO). In aMTO process, typically an oxygenated feedstock, most preferably amethanol containing feedstock, is converted in the presence of amolecular sieve catalyst composition into one or more olefin(s),preferably and predominantly, ethylene and/or propylene, often referredto as light olefin(s).

[0102] In one embodiment of the process for conversion of a feedstock,preferably a feedstock containing one or more oxygenates, the amount ofolefin(s) produced based on the total weight of hydrocarbon produced isgreater than 50 weight percent, preferably greater than 60 weightpercent, more preferably greater than 70 weight percent, and mostpreferably greater than 75 weight percent. In another embodiment of theprocess for conversion of one or more oxygenates to one or moreolefin(s), the amount of ethylene and/or propylene produced based on thetotal weight of hydrocarbon product produced is greater than 65 weightpercent, preferably greater than 70 weight percent, more preferablygreater than 75 weight percent, and most preferably greater than 78weight percent.

[0103] In another embodiment of the process for conversion of one ormore oxygenates to one or more olefin(s), the amount ethylene producedin weight percent based on the total weight of hydrocarbon productproduced, is greater than 30 weight percent, more preferably greaterthan 35 weight percent, and most preferably greater than 40 weightpercent. In yet another embodiment of the process for conversion of oneor more oxygenates to one or more olefin(s), the amount of propyleneproduced in weight percent based on the total weight of hydrocarbonproduct produced is greater than 20 weight percent, preferably greaterthan 25 weight percent, more preferably greater than 30 weight percent,and most preferably greater than 35 weight percent.

[0104] Increasing the selectivity of preferred hydrocarbon products suchas ethylene and/or propylene from the conversion of an oxygenate using amolecular sieve catalyst composition is described in U.S. Pat. No.6,137,022 (linear velocity), and PCT WO 00/74848 published Dec. 14, 2000(methanol uptake index of at least 0.13), which are all herein fullyincorporated by reference.

[0105] The feedstock, in one embodiment, contains one or morediluent(s), typically used to reduce the concentration of the feedstock,and are generally non-reactive to the feedstock or molecular sievecatalyst composition. Non-limiting examples of diluents include helium,argon, nitrogen, carbon monoxide, carbon dioxide, water, essentiallynon-reactive paraffins (especially alkanes such as methane, ethane, andpropane), essentially non-reactive aromatic compounds, and mixturesthereof. The most preferred diluents are water and nitrogen, with waterbeing particularly preferred.

[0106] The diluent, water, is used either in a liquid or a vapor form,or a combination thereof. The diluent is either added directly to afeedstock entering into a reactor or added directly into a reactor, oradded with a molecular sieve catalyst composition. In one embodiment,the amount of diluent in the feedstock is in the range of from about 1to about 99 mole percent based on the total number of moles of thefeedstock and diluent, preferably from about 1 to 80 mole percent, morepreferably from about 5 to about 50, most preferably from about 5 toabout 25. In one embodiment, other hydrocarbons are added to a feedstockeither directly or indirectly, and include olefin(s), paraffin(s),aromatic(s) (see for example U.S. Pat. No. 4,677,242, addition ofaromatics) or mixtures thereof, preferably propylene, butylene,pentylene, and other hydrocarbons having 4 or more carbon atoms, ormixtures thereof.

[0107] The process for converting a feedstock, especially a feedstockcontaining one or more oxygenates, in the presence of a molecular sievecatalyst composition of the invention, is carried out in a reactionprocess in a reactor, where the process is a fixed bed process, afluidized bed process (includes a turbulent bed process), preferably acontinuous fluidized bed process, and most preferably a continuous highvelocity fluidized bed process.

[0108] The reaction processes can take place in a variety of catalyticreactors such as hybrid reactors that have a dense bed or fixed bedreaction zones and/or fast fluidized bed reaction zones coupledtogether, circulating fluidized bed reactors, riser reactors, and thelike. Suitable conventional reactor types are described in for exampleU.S. Pat. No. 4,076,796, U.S. Pat. No. 6,287,522 (dual riser), andFluidization Engineering, D. Kunii and O. Levenspiel, Robert E. KriegerPublishing Company, New York, N.Y. 1977, which are all herein fullyincorporated by reference.

[0109] The preferred reactor type are riser reactors generally describedin Riser Reactor, Fluidization and Fluid-Particle Systems, pages 48 to59, F. A. Zenz and D. F. Othmo, Reinhold Publishing Corporation, NewYork, 1960, and U.S. Pat. No. 6,166,282 (fast-fluidized bed reactor),and U.S. patent application Ser. No. 09/564,613 filed May 4, 2000(multiple riser reactor), which are all herein fully incorporated byreference.

[0110] In the preferred embodiment, a fluidized bed process or highvelocity fluidized bed process includes a reactor system, a regenerationsystem and a recovery system.

[0111] The reactor system preferably is a fluid bed reactor systemhaving a first reaction zone within one or more riser reactor(s) and asecond reaction zone within at least one disengaging vessel, preferablycomprising one or more cyclones. In one embodiment, the one or moreriser reactor(s) and disengaging vessel is contained within a singlereactor vessel. Fresh feedstock, preferably containing one or moreoxygenates, optionally with one or more diluent(s), is fed to the one ormore riser reactor(s) in which a zeolite or zeolite-type molecular sievecatalyst composition or coked version thereof is introduced. In oneembodiment, the molecular sieve catalyst composition or coked versionthereof is contacted with a liquid or gas, or combination thereof, priorto being introduced to the riser reactor(s), preferably the liquid iswater or methanol, and the gas is an inert gas such as nitrogen.

[0112] In an embodiment, the amount of fresh feedstock fed separately orjointly with a vapor feedstock, to a reactor system is in the range offrom 0.1 weight percent to about 85 weight percent, preferably fromabout 1 weight percent to about 75 weight percent, more preferably fromabout 5 weight percent to about 65 weight percent based on the totalweight of the feedstock including any diluent contained therein. Theliquid and vapor feedstocks are preferably the same composition, orcontain varying proportions of the same or different feedstock with thesame or different diluent.

[0113] The feedstock entering the reactor system is preferablyconverted, partially or fully, in the first reactor zone into a gaseouseffluent that enters the disengaging vessel along with a coked molecularsieve catalyst composition. In the preferred embodiment, cyclone(s)within the disengaging vessel are designed to separate the molecularsieve catalyst composition, preferably a coked molecular sieve catalystcomposition, from the gaseous effluent containing one or more olefin(s)within the disengaging zone. Cyclones are preferred, however, gravityeffects within the disengaging vessel will also separate the catalystcompositions from the gaseous effluent. Other methods for separating thecatalyst compositions from the gaseous effluent include the use ofplates, caps, elbows, and the like.

[0114] In one embodiment of the disengaging system, the disengagingsystem includes a disengaging vessel, typically a lower portion of thedisengaging vessel is a stripping zone. In the stripping zone the cokedmolecular sieve catalyst composition is contacted with a gas, preferablyone or a combination of steam, methane, carbon dioxide, carbon monoxide,hydrogen, or an inert gas such as argon, preferably steam, to recoveradsorbed hydrocarbons from the coked molecular sieve catalystcomposition that is then introduced to the regeneration system. Inanother embodiment, the stripping zone is in a separate vessel from thedisengaging vessel and the gas is passed at a gas hourly superficialvelocity (GHSV) of from 1 hr⁻¹ to about 20,000 hr⁻¹ based on the volumeof gas to volume of coked molecular sieve catalyst composition,preferably at an elevated temperature from 250° C. to about 750° C.,preferably from about 350° C. to 650° C., over the coked molecular sievecatalyst composition.

[0115] The conversion temperature employed in the conversion process,specifically within the reactor system, is in the range of from about200° C. to about 1000° C., preferably from about 250° C. to about 800°C., more preferably from about 250° C. to about 750° C., yet morepreferably from about 300° C. to about 650° C., yet even more preferablyfrom about 350° C. to about 600° C. most preferably from about 350° C.to about 550° C.

[0116] The conversion pressure employed in the conversion process,specifically within the reactor system, varies over a wide rangeincluding autogenous pressure. The conversion pressure is based on thepartial pressure of the feedstock exclusive of any diluent therein.Typically the conversion pressure employed in the process is in therange of from about 0.1 kPaa to about 5 MPaa, preferably from about 5kPaa to about 1 MPaa, and most preferably from about 20 kPaa to about500 kPaa.

[0117] The weight hourly space velocity (WHSV), particularly in aprocess for converting a feedstock containing one or more oxygenates inthe presence of a molecular sieve catalyst composition within a reactionzone, is defined as the total weight of the feedstock excluding anydiluents to the reaction zone per hour per weight of molecular sieve inthe molecular sieve catalyst composition in the reaction zone. The WHSVis maintained at a level sufficient to keep the catalyst composition ina fluidized state within a reactor.

[0118] Typically, the WHSV ranges from about 1 hr⁻¹ to about 5000 hr⁻¹,preferably from about 2 hr⁻¹ to about 3000 hr⁻¹, more preferably fromabout 5 hr⁻¹ to about 1500 hr⁻¹, and most preferably from about 10 hr⁻¹to about 1000 hr⁻¹. In one preferred embodiment, the WHSV is greaterthan 20 hr⁻¹, preferably the WHSV for conversion of a feedstockcontaining methanol and dimethyl ether is in the range of from about 20hr⁻¹ to about 300 hr⁻¹.

[0119] The superficial gas velocity (SGV) of the feedstock includingdiluent and reaction products within the reactor system is preferablysufficient to fluidize the molecular sieve catalyst composition within areaction zone in the reactor. The SGV in the process, particularlywithin the reactor system, more particularly within the riserreactor(s), is at least 0.1 meter per second (m/sec), preferably greaterthan 0.5 m/sec, more preferably greater than 1 m/sec, even morepreferably greater than 2 m/sec, yet even more preferably greater than 3m/sec, and most preferably greater than 4 m/sec. See for example U.S.patent application Ser. No. 09/708,753 filed Nov. 8, 2000, which isherein incorporated by reference.

[0120] In one preferred embodiment of the process for converting anoxygenate to olefin(s) using a silicoaluminophosphate molecular sievecatalyst composition, the process is operated at a WHSV of at least 20hr⁻¹ and a Temperature Corrected Normalized Methane Selectivity (TCNMS)of less than 0.016, preferably less than or equal to 0.01. See forexample U.S. Pat. No. 5,952,538, which is herein fully incorporated byreference.

[0121] In another embodiment of the processes for converting anoxygenate such as methanol to one or more olefin(s) using a molecularsieve catalyst composition, the WHSV is from 0.01 hr⁻¹ to about 100hr⁻¹, at a temperature of from about 350° C. to 550° C., and silica toMe₂O₃ (Me is a Group IIIA or VIII element from the Periodic Table ofElements) molar ratio of from 300 to 2500. See for example EP-0 642 485B1, which is herein fully incorporated by reference.

[0122] Other processes for converting an oxygenate such as methanol toone or more olefin(s) using a molecular sieve catalyst composition aredescribed in PCT WO 01/23500 published Apr. 5, 2001 (propane reductionat an average catalyst feedstock exposure of at least 1.0), which isherein incorporated by reference.

[0123] The coked molecular sieve catalyst composition is withdrawn fromthe disengaging vessel, preferably by one or more cyclones(s), andintroduced to the regeneration system. The regeneration system comprisesa regenerator where the coked catalyst composition is contacted with aregeneration medium, preferably a gas containing oxygen, under generalregeneration conditions of temperature, pressure and residence time.

[0124] Non-limiting examples of the regeneration medium include one ormore of oxygen, O₃, SO₃, N₂O, NO, NO₂, N₂O₅, air, air diluted withnitrogen or carbon dioxide, oxygen and water (U.S. Pat. No. 6,245,703),carbon monoxide and/or hydrogen. The regeneration conditions are thosecapable of burning coke from the coked catalyst composition, preferablyto a level less than 0.5 weight percent based on the total weight of thecoked molecular sieve catalyst composition entering the regenerationsystem. The coked molecular sieve catalyst composition withdrawn fromthe regenerator forms a regenerated molecular sieve catalystcomposition.

[0125] The regeneration temperature is in the range of from about 200°C. to about 1500° C., preferably from about 300° C. to about 1000° C.,more preferably from about 450° C. to about 750° C., and most preferablyfrom about 550° C. to 700° C. The regeneration pressure is in the rangeof from about 15 psia (103 kPaa) to about 500 psia (3448 kPaa),preferably from about 20 psia (138 kPaa) to about 250 psia (1724 kPaa),more preferably from about 25 psia (172 kPaa) to about 150 psia (1034kPaa), and most preferably from about 30 psia (207 kPaa) to about 60psia (414 kPaa).

[0126] The preferred residence time of the molecular sieve catalystcomposition in the regenerator is in the range of from about one minuteto several hours, most preferably about one minute to 100 minutes, andthe preferred volume of oxygen in the gas is in the range of from about0.01 mole percent to about 5 mole percent based on the total volume ofthe gas.

[0127] In one embodiment, regeneration promoters, typically metalcontaining compounds such as platinum, palladium and the like, are addedto the regenerator directly, or indirectly, for example with the cokedcatalyst composition. Also, in another embodiment, a fresh molecularsieve catalyst composition is added to the regenerator containing aregeneration medium of oxygen and water as described in U.S. Pat. No.6,245,703, which is herein fully incorporated by reference.

[0128] In an embodiment, a portion of the coked molecular sieve catalystcomposition from the regenerator is returned directly to the one or moreriser reactor(s), or indirectly, by pre-contacting with the feedstock,or contacting with fresh molecular sieve catalyst composition, orcontacting with a regenerated molecular sieve catalyst composition or acooled regenerated molecular sieve catalyst composition described below.

[0129] The burning of coke is an exothermic reaction, and in anembodiment, the temperature within the regeneration system is controlledby various techniques in the art including feeding a cooled gas to theregenerator vessel, operated either in a batch, continuous, orsemi-continuous mode, or a combination thereof. A preferred techniqueinvolves withdrawing the regenerated molecular sieve catalystcomposition from the regeneration system and passing the regeneratedmolecular sieve catalyst composition through a catalyst cooler thatforms a cooled regenerated molecular sieve catalyst composition. Thecatalyst cooler, in an embodiment, is a heat exchanger that is locatedeither internal or external to the regeneration system.

[0130] In one embodiment, the cooler regenerated molecular sievecatalyst composition is returned to the regenerator in a continuouscycle, alternatively, (see U.S. patent application Ser. No. 09/587,766filed Jun. 6, 2000) a portion of the cooled regenerated molecular sievecatalyst composition is returned to the regenerator vessel in acontinuous cycle, and another portion of the cooled molecular sieveregenerated molecular sieve catalyst composition is returned to theriser reactor(s), directly or indirectly, or a portion of theregenerated molecular sieve catalyst composition or cooled regeneratedmolecular sieve catalyst composition is contacted with by-productswithin the gaseous effluent (PCT WO 00/49106 published Aug. 24, 2000),which are all herein fully incorporated by reference. In anotherembodiment, a regenerated molecular sieve catalyst composition contactedwith an alcohol, preferably ethanol, 1-propnaol, 1-butanol or mixturethereof, is introduced to the reactor system, as described in U.S.patent application Ser. No. 09/785,122 filed Feb. 16, 2001, which isherein fully incorporated by reference.

[0131] Other methods for operating a regeneration system are indisclosed U.S. Pat. No. 6,290,916 (controlling moisture), which isherein fully incorporated by reference.

[0132] The regenerated molecular sieve catalyst composition withdrawnfrom the regeneration system, preferably from the catalyst cooler, iscombined with a fresh molecular sieve catalyst composition and/orre-circulated molecular sieve catalyst composition and/or feedstockand/or fresh gas or liquids, and returned to the riser reactor(s). Inanother embodiment, the regenerated molecular sieve catalyst compositionwithdrawn from the regeneration system is returned to the riserreactor(s) directly, preferably after passing through a catalyst cooler.In one embodiment, a carrier, such as an inert gas, feedstock vapor,steam or the like, semi-continuously or continuously, facilitates theintroduction of the regenerated molecular sieve catalyst composition tothe reactor system, preferably to the one or more riser reactor(s).

[0133] By controlling the flow of the regenerated molecular sievecatalyst composition or cooled regenerated molecular sieve catalystcomposition from the regeneration system to the reactor system, theoptimum level of coke on the molecular sieve catalyst compositionentering the reactor is maintained. There are many techniques forcontrolling the flow of a molecular sieve catalyst composition describedin Michael Louge, Experimental Techniques, Circulating Fluidized Beds,Grace, Avidan and Knowlton, eds., Blackie, 1997 (336-337), which isherein incorporated by reference.

[0134] Coke levels on the molecular sieve catalyst composition ismeasured by withdrawing from the conversion process the molecular sievecatalyst composition at a point in the process and determining itscarbon content. Typical levels of coke on the molecular sieve catalystcomposition, after regeneration is in the range of from 0.01 weightpercent to about 15 weight percent, preferably from about 0.1 weightpercent to about 10 weight percent, more preferably from about 0.2weight percent to about 5 weight percent, and most preferably from about0.3 weight percent to about 2 weight percent based on the total weightof the molecular sieve and not the total weight of the molecular sievecatalyst composition.

[0135] In one preferred embodiment, the mixture of fresh molecular sievecatalyst composition and regenerated molecular sieve catalystcomposition and/or cooled regenerated molecular sieve catalystcomposition contains in the range of from about 1 to 50 weight percent,preferably from about 2 to 30 weight percent, more preferably from about2 to about 20 weight percent, and most preferably from about 2 to about10 coke or carbonaceous deposit based on the total weight of the mixtureof molecular sieve catalyst compositions. See for example U.S. Pat. No.6,023,005, which is herein fully incorporated by reference.

[0136] The gaseous effluent is withdrawn from the disengaging system andis passed through a recovery system. There are many well known recoverysystems, techniques and sequences that are useful in separatingolefin(s) and purifying olefin(s) from the gaseous effluent. Recoverysystems generally comprise one or more or a combination of a variousseparation, fractionation and/or distillation towers, columns,splitters, or trains, reaction systems such as ethylbenzene manufacture(U.S. Pat. No. 5,476,978) and other derivative processes such asaldehydes, ketones and ester manufacture (U.S. Pat. No. 5,675,041), andother associated equipment for example various condensers, heatexchangers, refrigeration systems or chill trains, compressors,knock-out drums or pots, pumps, and the like.

[0137] Non-limiting examples of these towers, columns, splitters ortrains used alone or in combination include one or more of ademethanizer, preferably a high temperature demethanizer, a dethanizer,a depropanizer, preferably a wet depropanizer, a wash tower oftenreferred to as a caustic wash tower and/or quench tower, absorbers,adsorbers, membranes, ethylene (C2) splitter, propylene (C3) splitter,butene (C4) splitter, and the like.

[0138] Various recovery systems useful for recovering predominatelyolefin(s), preferably prime or light olefin(s) such as ethylene,propylene and/or butene are described in U.S. Pat. No. 5,960,643(secondary rich ethylene stream), U.S. Pat. Nos. 5,019,143, 5,452,581and 5,082,481 (membrane separations), U.S. Pat. No. 5,672,197 (pressuredependent adsorbents), U.S. Pat. No. 6,069,288 (hydrogen removal), U.S.Pat. No. 5,904,880 (recovered methanol to hydrogen and carbon dioxide inone step), U.S. Pat. No. 5,927,063 (recovered methanol to gas turbinepower plant), and U.S. Pat. No. 6,121,504 (direct product quench), U.S.Pat. No. 6,121,503 (high purity olefins without superfractionation), andU.S. Pat. No. 6,293,998 (pressure swing adsorption), which are allherein fully incorporated by reference.

[0139] Generally accompanying most recovery systems is the production,generation or accumulation of additional products, by-products and/orcontaminants along with the preferred prime products. The preferredprime products, the light olefins, such as ethylene and propylene, aretypically purified for use in derivative manufacturing processes such aspolymerization processes. Therefore, in the most preferred embodiment ofthe recovery system, the recovery system also includes a purificationsystem. For example, the light olefin(s) produced particularly in a MTOprocess are passed through a purification system that removes low levelsof by-products or contaminants.

[0140] Non-limiting examples of contaminants and by-products includegenerally polar compounds such as water, alcohols, carboxylic acids,ethers, carbon oxides, sulfur compounds such as hydrogen sulfide,carbonyl sulfides and mercaptans, ammonia and other nitrogen compounds,arsine, phosphine and chlorides. Other contaminants or by-productsinclude hydrogen and hydrocarbons such as acetylene, methyl acetylene,propadiene, butadiene and butyne.

[0141] Other recovery systems that include purification systems, forexample for the purification of olefin(s), are described in Kirk-OthmerEncyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley &Sons, 1996, pages 249-271 and 894-899, which is herein incorporated byreference. Purification systems are also described in for example, U.S.Pat. No. 6,271,428 (purification of a diolefin hydrocarbon stream), U.S.Pat. No. 6,293,999 (separating propylene from propane), and U.S. patentapplication Ser. No. 09/689,363 filed Oct. 20, 2000 (purge stream usinghydrating catalyst), which is herein incorporated by reference.

[0142] Typically, in converting one or more oxygenates to olefin(s)having 2 or 3 carbon atoms, an amount of hydrocarbons, particularlyolefin(s), especially olefin(s) having 4 or more carbon atoms, and otherby-products are formed or produced. Included in the recovery systems ofthe invention are reaction systems for converting the products containedwithin the effluent gas withdrawn from the reactor or converting thoseproducts produced as a result of the recovery system utilized.

[0143] In one embodiment, the effluent gas withdrawn from the reactor ispassed through a recovery system producing one or more hydrocarboncontaining stream(s), in particular, a three or more carbon atom (C₃ ⁺)hydrocarbon containing stream. In this embodiment, the C₃ ⁺ hydrocarboncontaining stream is passed through a first fractionation zone producinga crude C₃ hydrocarbon and a C₄ ⁺ hydrocarbon containing stream, the C₄⁺ hydrocarbon containing stream is passed through a second fractionationzone producing a crude C₄ hydrocarbon and a C₅ ⁺ hydrocarbon containingstream. The four or more carbon hydrocarbons include butenes such asbutene-1 and butene-2, butadienes, saturated butanes, and isobutanes.

[0144] The effluent gas removed from a conversion process, particularlya MTO process, typically has a minor amount of hydrocarbons having 4 ormore carbon atoms. The amount of hydrocarbons having 4 or more carbonatoms is typically in an amount less than 20 weight percent, preferablyless than 10 weight percent, more preferably less than 5 weight percent,and most preferably less than 2 weight percent, based on the totalweight of the effluent gas withdrawn from a MTO process, excludingwater. In particular with a conversion process of oxygenates intoolefin(s) utilizing a molecular sieve catalyst composition the resultingeffluent gas typically comprises a majority of ethylene and/or propyleneand a minor amount of four carbon and higher carbon number products andother by-products, excluding water.

[0145] Suitable well known reaction systems as part of the recoverysystem primarily take lower value products and convert them to highervalue products. For example, the C₄ hydrocarbons, butene-1 and butene-2are used to make alcohols having 8 to 13 carbon atoms, and otherspecialty chemicals, isobutylene is used to make a gasoline additive,methyl-t-butylether, butadiene in a selective hydrogenation unit isconverted into butene-1 and butene-2, and butane is useful as a fuel.

[0146] Non-limiting examples of reaction systems include U.S. Pat. No.5,955,640 (converting a four carbon product into butene-1), U.S. Pat.No. 4,774,375 (isobutane and butene-2 oligomerized to an alkylategasoline), U.S. Pat. No. 6,049,017 (dimerization of n-butylene), U.S.Pat. Nos. 4,287,369 and 5,763,678 (carbonylation or hydroformulation ofhigher olefins with carbon dioxide and hydrogen making carbonylcompounds), U.S. Pat. No. 4,542,252 (multistage adiabatic process), U.S.Pat. No. 5,634,354 (olefin-hydrogen recovery), and Cosyns, J. et al.,Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet. & Coal, Vol.37, No. 4 (1995) (dimerizing or oligomerizing propylene, butylene andpentylene), which are all herein fully incorporated by reference.

[0147] The preferred light olefin(s) produced by any one of theprocesses described above, preferably conversion processes, are highpurity prime olefin(s) products that contains a single carbon numberolefin in an amount greater than 80 percent, preferably greater than 90weight percent, more preferably greater than 95 weight percent, and mostpreferably no less than about 99 weight percent, based on the totalweight of the olefin.

[0148] In one embodiment, high purity prime olefin(s) are produced inthe process of the invention at rate of greater than 5 kg per day,preferably greater than 10 kg per day, more preferably greater than 20kg per day, and most preferably greater than 50 kg per day. In anotherembodiment, high purity ethylene and/or high purity propylene isproduced by the process of the invention at a rate greater than 4,500 kgper day, preferably greater than 100,000 kg per day, more preferablygreater than 500,000 kg per day, even more preferably greater than1,000,000 kg per day, yet even more preferably greater than 1,500,000 kgper day, still even more preferably greater than 2,000,000 kg per day,and most preferably greater than 2,500,000 kg per day.

[0149] Other conversion processes, in particular, a conversion processof an oxygenate to one or more olefin(s) in the presence of a molecularsieve catalyst composition, especially where the molecular sieve issynthesized from a silicon-, phosphorous-, and alumina-source, includethose described in for example: U.S. Pat. No. 6,121,503 (making plasticwith an olefin product having a paraffin to olefin weight ratio lessthan or equal to 0.05), U.S. Pat. No. 6,187,983 (electromagnetic energyto reaction system), PCT WO 99/18055 publishes Apr. 15, 1999 (heavyhydrocarbon in effluent gas fed to another reactor) PCT WO 01/60770published Aug. 23, 2001 and U.S. patent application Ser. No. 09/627,634filed Jul. 28, 2000 (high pressure), U.S. patent application Ser. No.09/507,838 filed Feb. 22, 2000 (staged feedstock injection), and U.S.patent application Ser. No. 09/785,409 filed Feb. 16, 2001 (acetoneco-fed), which are all herein fully incorporated by reference.

[0150] In an embodiment, an integrated process is directed to producinglight olefin(s) from a hydrocarbon feedstock, preferably a hydrocarbongas feedstock, more preferably methane and/or ethane. The first step inthe process is passing the gaseous feedstock, preferably in combinationwith a water stream, to a syngas production zone to produce a synthesisgas (syngas) stream. Syngas production is well known, and typical syngastemperatures are in the range of from about 700° C. to about 1200° C.and syngas pressures are in the range of from about 2 MPa to about 100MPa. Synthesis gas streams are produced from natural gas, petroleumliquids, and carbonaceous materials such as coal, recycled plastic,municipal waste or any other organic material, preferably synthesis gasstream is produced via steam reforming of natural gas.

[0151] Generally, a heterogeneous catalyst, typically a copper basedcatalyst, is contacted with a synthesis gas stream, typically carbondioxide and carbon monoxide and hydrogen to produce an alcohol,preferably methanol, often in combination with water. In one embodiment,the synthesis gas stream at a synthesis temperature in the range of fromabout 150° C. to about 450° C. and at a synthesis pressure in the rangeof from about 5 MPa to about 10 MPa is passed through a carbon oxideconversion zone to produce an oxygenate containing stream.

[0152] This oxygenate containing stream, or crude methanol, typicallycontains the alcohol product and various other components such asethers, particularly dimethyl ether, ketones, aldehydes, dissolved gasessuch as hydrogen methane, carbon oxide and nitrogen, and fusel oil. Theoxygenate containing stream, crude methanol, in the preferred embodimentis passed through a well known purification processes, distillation,separation and fractionation, resulting in a purified oxygenatecontaining stream, for example, commercial Grade A and AA methanol.

[0153] The oxygenate containing stream or purified oxygenate containingstream, optionally with one or more diluents, is contacted with one ormore molecular sieve catalyst composition described above in any one ofthe processes described above to produce a variety of prime products,particularly light olefin(s), ethylene and/or propylene. Non-limitingexamples of this integrated process is described in EP-B-0 933 345,which is herein fully incorporated by reference.

[0154] In another more fully integrated process, optionally with theintegrated processes described above, olefin(s) produced are directedto, in one embodiment, one or more polymerization processes forproducing various polyolefins. (See for example U.S. patent applicationSer. No. 09/615,376 filed Jul. 13, 2000, which is herein fullyincorporated by reference.)

[0155] Polymerization processes include solution, gas phase, slurryphase and a high pressure processes, or a combination thereof.Particularly preferred is a gas phase or a slurry phase polymerizationof one or more olefin(s) at least one of which is ethylene or propylene.Polymerization processes include those non-limiting examples describedin the following: U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661, 5,627,242, 5,665,818, 5,677,375, 5,668,228, 5,712,352 and5,763,543 and EP-A-0 794 200, EP-A-0 802 202, EP-A2-0 891 990 and EP-B-0634 421 describe gas phase polymerization processes; U.S. Pat. Nos.3,248,179 and 4,613,484, 6,204,344, 6,239,235 and 6,281,300 describeslurry phase polymerization processes; U.S. Pat. Nos. 4,271,060,5,001,205, 5,236,998 and 5,589,555 describe solution phasepolymerization processes; and U.S. Pat. Nos. 3,917,577, 4,175,169,4,935,397, and 6,127,497 describe high pressure polymerizationprocesses; all of which are herein fully incorporated by reference.

[0156] These polymerization processes utilize a polymerization catalystthat can include any one or a combination of the molecular sievecatalysts discussed above, however, the preferred polymerizationcatalysts are those Ziegler-Natta, Phillips-type, metallocene,metallocene-type and advanced polymerization catalysts, and mixturesthereof. Non-limiting examples of polymerization catalysts are describedin U.S. Pat. Nos. 3,258,455, 3,305,538, 3,364,190, 3,645,992, 4,076,698,4,115,639, 4,077,904 4,482,687, 4,564,605, 4,659,685, 4,721,763,4,879,359, 4,960,741, 4,302,565, 4,302,566, 4,302,565, 4,302,566,4,124,532, 4,302,565, 5,763,723, 4,871,705, 5,120,867, 5,324,800,5,347,025, 5,384,299, 5,391,790, 5,408,017, 5,491,207, 5,455,366,5,534,473, 5,539,124, 5,554,775, 5,621,126, 5,684,098, 5,693,730,5,698,634, 5,710,297, 5,714,427, 5,728,641, 5,728,839, 5,753,577,5,767,209, 5,770,753 and 5,770,664, 5,527,752, 5,747,406, 5,851,945 and5,852,146, all of which are herein fully incorporated by reference.

[0157] In preferred embodiment, the integrated process comprises apolymerizing process of one or more olefin(s) in the presence of apolymerization catalyst system in a polymerization reactor to produceone or more polymer products, wherein the one or more olefin(s) havingbeen made by converting an alcohol, particularly methanol, using azeolite or zeolite-type molecular sieve catalyst composition. Thepreferred polymerization process is a gas phase polymerization processand at least one of the olefins(s) is either ethylene or propylene, andpreferably the polymerization catalyst system is a supported metallocenecatalyst system. In this embodiment, the supported metallocene catalystsystem comprises a support, a metallocene or metallocene-type compoundand an activator, preferably the activator is a non-coordinating anionor alumoxane, or combination thereof, and most preferably the activatoris alumoxane.

[0158] Polymerization conditions vary depending on the polymerizationprocess, polymerization catalyst system and the polyolefin produced.Typical conditions of polymerization pressure vary from about 100 psig(690 kPag) to greater than about 1000 psig (3448 kPag), preferably inthe range of from about 200 psig (1379 kPag) to about 500 psig (3448kPag), and more preferably in the range of from about 250 psig (1724kPag) to about 350 psig (2414 kPag). Typical conditions ofpolymerization temperature vary from about 0° C. to about 500° C.,preferably from about 30° C. to about 350° C., more preferably in therange of from about 60° C. to 250° C., and most preferably in the rangeof from about 70° C. to about 150° C. In the preferred polymerizationprocess the amount of polymer being produced per hour is greater than25,000 lbs/hr (11,300 Kg/hr), preferably greater than 35,000 lbs/hr(15,900 Kg/hr), more preferably greater than 50,000 lbs/hr (22,700Kg/hr) and most preferably greater than 75,000 lbs/hr (29,000 Kg/hr).

[0159] The polymers produced by the polymerization processes describedabove include linear low density polyethylene, elastomers, plastomers,high density polyethylene, low density polyethylene, polypropylene andpolypropylene copolymers. The propylene based polymers produced by thepolymerization processes include atactic polypropylene, isotacticpolypropylene, syndiotactic polypropylene, and propylene random, blockor impact copolymers.

[0160] Typical ethylene based polymers have a density in the range offrom 0.86 g/cc to 0.97 g/cc, a weight average molecular weight to numberaverage molecular weight (M_(w)/M_(n)) of greater than 1.5 to about 10as measured by gel permeation chromatography, a melt index (I₂) asmeasured by ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min,a melt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from10 to less than 25, alternatively a I₂₁/I₂ of from greater than 25, morepreferably greater than 40.

[0161] Polymers produced by the polymerization process are useful insuch forming operations as film, sheet, and fiber extrusion andco-extrusion as well as blow molding, injection molding and rotarymolding; films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications;fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc; extruded articles includemedical tubing, wire and cable coatings, geomembranes, and pond liners;and molded articles include single and multi-layered constructions inthe form of bottles, tanks, large hollow articles, rigid food containersand toys, etc.

[0162] In addition to polyolefins, numerous other olefin derivedproducts are formed from the olefin(s) recovered any one of theprocesses described above, particularly the conversion processes, moreparticularly the GTO process or MTO process. These include, but are notlimited to, aldehydes, alcohols, acetic acid, linear alpha olefins,vinyl acetate, ethylene dicholoride and vinyl chloride, ethylbenzene,ethylene oxide, cumene, isopropyl alcohol, acrolein, allyl chloride,propylene oxide, acrylic acid, ethylene-propylene rubbers, andacrylonitrile, and trimers and dimers of ethylene, propylene orbutylenes.

EXAMPLES

[0163] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples are offered.

Comparative Example 1 Preparation of Molecular Sieve Two Mole TEAOH perMole of P₂O₅

[0164] Following a typical SAPO-34 synthesis, the a silicon source, aphosphorous source and an aluminum source and a templating agent weremixed according to the following molar ratio:

[0165] 2.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O to form a reactionmixture. The sources of the ingredients were pseudo-boehmite (analuminum source), 85% phosphoric acid (a phosphorous source), LUDOXHS-40 (a silicon source), and 40% aqueous solution of TEAOH (an organictemplating agent). The order of mixing was first adding H₃PO₄, then H₂O,followed by Ludox, then Pseudo-boehmite, and finally TEAOH in the molarproportions described above. The reaction mixture was then blended intoa uniform gel using a microhomogenizer. The gel was then placed into aParr bomb with a Teflon liner, and was heated to 180° C. for six days.The solid product formed was centrifuged and washed several times withdeionized water, and was then dried in a 60° C. vacuum oven overnight.The XRD, X-ray powder pattern, of the product confirms that the productis a pure SAPO-34 and having an elemental analysis of the followingmolar composition: Al_(1.0)Si_(0.173)P_(0.834).

Example 2 Preparation of Molecular Sieve Using Polyethylenimine (PEI)Replacing Some TEAOH

[0166] Polyethylenimine (available from Aldrich Chemical Company, Inc.,Milwaukee, Wis.) described as(—NHCH₂CH₂—)_(x)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(y)) in a 50 weight percent (wt%) aqueous solution, and having average molecular weight (M_(w)) of750,000, was diluted with water to a 25 wt % solution. The sources ofphosphorous, silicon, aluminum, polymeric base, and templating agentwere added according to the following order: first the phosphoroussource, H₃PO₄, then H₂O, then the silicon source, Ludox, followed by thealuminum source, pseudo-boehmite, then the polymeric base, PEI, andlastly the templating agent, TEAOH. The reaction mixture was blendedusing a microhomogenizer. When higher amount of the polymeric base, PEI,was used, the gel had the consistency of a soft gum coexisting with aclear liquid. The molar ratios of ingredients for three preparationswere as follows:

[0167] (1)2.0 PEI monomeric unit(CH₂CH₂NH):1.5TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

[0168] (2)4.0 PEI monomeric unit(CH₂CH₂NH):1.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

[0169] (3)6.0 PEI monomeric unit(CH₂CH₂NH):0.5TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

[0170] Each reaction mixture, individually, were sealed in a Teflonlined Parr bomb and were heated to 180° C. for seven days. The solidproduct formed were centrifuged and washed several times with deionizedwater, and then dried in a 60° C. vacuum oven. The X-ray powderdiffraction patterns of the three molecular sieves synthesized,preparations 1 and 2 produced pure a SAPO-34 phase, while preparation 3produced a SAPO-34 molecular sieve plus an unidentified phase having twobroad peaks at around 15 Å and 7.5 Å d-spacings.

Example 3 Preparation of a Molecular Sieve with One Mole Equivalent ofPolyethylenimine (PEI) Replacing One Mole of TEAOH.

[0171] The same procedure as described in Example 1 was used except themole ratio of the sources of silicon, aluminum, and phosphorous, thetemplating agent, and polymeric base, were as follows:

[0172] (4)1.0 PEI monomeric unit(CH₂CH₂NH):1.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

[0173] The reaction mixture was homogenized, sealed in a Teflon linedParr bomb and then heated to 180° C. (hydrothermal reaction temperature)for thirteen days. The solid product formed was centrifuged and washedseveral times with deionized water, and was dried in a 60° C. vacuumoven. The X-ray powder diffraction pattern indicated pure SAPO-34 wasobtained. The SAPO-34 yield was 17.5 wt %, based on the total weight ofthe starting materials. Elemental analysis showed: Al, 16.5%; Si, 2.76%;P, 16.0% corresponding to the composition: Al_(1.0)Si_(0.161)P_(0.845).

Example 4 Preparation of Molecular Sieve Using One Mole Equivalent ofPolyethylenimine (PEI) Replacing One Mole of TEAOH, at 200° C.

[0174] The same synthesis procedure as described in Example 3 above wasused except that the hydrothermal reaction temperature was set at 200°C. Crystallization proceeded for 5 days. The XRD of the molecular sieveproduct showed a highly crystalline SAPO-34 with a minor amount of anunidentified crystalline impurity. The molecular sieve solid yield was17.0 wt %, based on the total weight of the starting materials. ThisExample 4 illustrates that crystallization time is dramatically reducedby increasing the hydrothermal synthesis reaction temperature.

Example 5 Preparation of Molecular Sieve Using Three Mole Equivalent ofPolyethylenimine (PEI) and One Mole of N,N,N-trimethyladamantylammoniumiodide, at 180° C.

[0175] 2.07 g H₃PO₄(75%), 3.17 g H₂O, 1.08 g pseudo-boehmite, 0.16 gfumed silica, 4.03 g polyethylenimine (PEI), and 2.50 gN,N,N-trimethyladamantylammonium iodide was added, in sequence withvigorous blending. The molar ratios of the ingredients are thefollowing:

[0176] (5) 3.0(CH₂CH₂NH):1.0R⁺I⁻:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O, whereR⁺I⁻ is N,N,N-trimethyladamantylammonium iodide.

[0177] In one embodiment, a molecular sieve, most preferably a SAPOmolecular sieve, even more particularly a SAPO-34 molecular sieve, isformed using the templating agent, N,N,N-trimethyladamantylammoniumiodide. The mixture was sealed, and crystallization carried out, asdescribed above in Example 4. After 4 days of crystallization thecrystalline molecular sieve was isolated by centrifugation and waswashed with deionized water. The XRD of the solid product indicated thatpure SAPO-34 (CHA structure-type) was obtained. The molecular sievesolid yield was 19.3 wt % based on the total weight of the startingmaterials. This example illustrates the use of a quaternary ammoniumiodide salt as the templating agent, instead of the more expensivequaternary ammonium hydroxide, when a polymeric base is used to controlthe pH.

[0178] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that themolecular sieve catalyst composition is useful in the inter-conversionof olefin(s), oxygenate to gasoline conversions reactions, malaeicanhydride, phthalic anyhdride and acrylonitrile formulation, vapor phasemethanol synthesis, and various Fischer Tropsch reactions. It is furthercontemplated that a plug flow, fixed bed or fluidized bed process areused in combination, particularly in different reaction zones within asingle or multiple reactor system. It is also contemplated the molecularsieves described herein are useful as absorbents, adsorbents, gasseparators, detergents, water purifiers, and other various uses such asagriculture and horticulture. For this reason, then, reference should bemade solely to the appended claims for purposes of determining the truescope of the present invention.

We claim:
 1. A method for synthesizing a molecular sieve, the methodcomprising the steps of: (a) forming a reaction mixture comprising: atleast one templating agent and at least two of the group consisting of asilicon source, a phosphorous source and an aluminum source; (b)introducing to the reaction mixture a polymeric base; and (c) recoveringthe molecular sieve from the reaction mixture.
 2. The method claim 1wherein the polymeric base is a soluble polymeric base.
 3. The method ofclaim 1 wherein the polymeric base is a polymeric imine.
 4. The methodof claim 1 wherein the polymeric base is represented by the formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n)), wherein m is from 10 to20,000, and n is from 1 to 2,000.
 5. The method claim 1 wherein the moleratio of the monomeric unit of the polymeric base to the templatingagent is less than
 20. 6. The method of claim 1 wherein the reactionmixture is maintained at a pH in the range of from 3 to
 10. 7. Themethod of claim 1 wherein the templating agent is a quaternary ammoniumhydroxide or a quaternary ammonium salt.
 8. The method of claim 1wherein the polymeric base is selected from on the group consisting of:epichlorohydrin modified polyethylenimine, ethoxylated polyethylenimine,polypropylenimine diamine dendrimers, poly(allylamine),poly(1,2-dihydro-2,2,4-trimethylquinoline), andpoly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).
 9. The methodof claim 1 wherein the reaction mixture comprises: at least onetemplating agent and a silicon source, a phosphorous source and analuminum source.
 10. The method of claim 1 wherein the reaction mixturecomprises: at least one templating agent and a phosphorous source and analuminum source.
 11. A method for synthesizing a molecular sieve, themethod comprising the steps of: (a) combining at least one templatingagent and at least one of the group consisting of a silicon source, aphosphorous source and an aluminum source; and (b) adding a non-ionicpolymeric base.
 12. The method of claim 10 wherein the method furthercomprises the step of: (c) crystallizing the molecular sieve at atemperature less than 200° C.
 13. The method of claim 11 wherein thenon-ionic polymeric base is soluble.
 14. The method of claim 11 whereinthe non-ionic polymeric base is represented by the formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n)), wherein m is from 10 to20,000, and n is from 1 to 2,000.
 15. The method claim 11 wherein themole ratio of the monomeric unit of the non-ionic polymeric base to thetemplating agent is less than
 20. 16. The method of claim 15 wherein thenon-ionic polymeric base in an aqueous solution has a pH in the range offrom 8 to
 14. 17. The method of claim 11 wherein the templating agent isa quaternary ammonium hydroxide or a quaternary ammonium salt.
 18. Themethod of claim 11 wherein the at least templating agent is combinedwith a silicon source, a phosphorous source and an aluminum source. 19.The method of claim 1 wherein the non-ionic polymeric base is apolymeric imine.
 20. A molecular sieve catalyst composition comprising,in combination, at least one templating agent, at least one of the groupconsisting of a silicon source, a phosphorous source and an aluminumsource, and a polymeric base.
 21. The molecular sieve catalystcomposition of claim 20, wherein the molecular sieve catalystcomposition is dried.
 22. The molecular sieve catalyst composition ofclaim 20 wherein the molecular sieve catalyst composition comprises of asilicon source, a phosphorous source and an aluminum source.
 23. Amethod for forming a molecular sieve catalyst composition from themolecular sieve recovered in step (c) of claim 1, wherein the methodfurther comprises the step of: contacting the molecular sieve with amatrix material, optionally with a binder.
 24. The method of claim 23wherein the molecular sieve recovered is a SAPO molecular sieve.
 25. Themethod of claim 23 wherein the molecular sieve recovered is an ALPOmolecular sieve.
 26. The method of claim 23 wherein the molecular sievecatalyst composition is spray dried.
 27. A process for producing one ormore olefin(s), the process comprising the steps of: (a) introducing afeedstock to a reactor system in the presence of the molecular sieve ofclaim 1; (b) withdrawing from the reactor system an effluent stream; and(c) passing the effluent gas through a recovery system recovering atleast the one or more olefin(s).
 28. The process of claim 23 wherein theprocess further comprises the step of: (d) introducing the molecularsieve to a regeneration system to form a regenerated molecular sieve,and introducing the regenerated molecular sieve to the reaction system.29. An integrated process for making one or more olefin(s), theintegrated process comprising the steps of: (a) passing a hydrocarbonfeedstock to a syngas production zone to producing a synthesis gasstream; (b) contacting the synthesis gas stream with a catalyst to forman oxygenated feedstock; and (c) converting the oxygenated feedstock inthe presence of the molecular sieve of claim 1 into the one or moreolefin(s).
 30. The process of claim 29 wherein the process furthercomprises the step of (e) polymerizing the one or more olefin(s) in thepresence of a polymerization catalyst into a polyolefin.